Polyvinyl chloride composition containing hydrocarbon tar



F. P. #ORD ET AL POLYVINYL cHLORxOE COMPOSITION Aug. 9, 1960 CONTAINING HYOROCARBON TAR.

Filed sept. 17. 195s ummm .=o m5 Unite POLYVINYL CHLORIDE COMPOSITIGN CGNTAINING HYDROCARB'ON TAR Francis P. Ford, Roselle, NJ., Gabriel E. Jasper, Bronxville, N.Y., and Joseph F. Nelson, Westfield, and Lester M. Welch, Madison, NJ., assignors to Esso Research and Engineering Company, a corporation of.

This invention relates to a new class of materials which have been discovered to be particularly effective as plasticizers for resins and rubber-like materials. In particular, this invention relates to the use of thermally cracked catalytic cycle stocks as plasticizers.

The ever expanding use of plastic materials such as vinyl chloride polymers or copolymers, polyvinyl acetate, cellulose esters, acrylate and methacrylate resins, rubbers such as the emulsion copolymers of butadiene with styrene or vaerylonitrile, or the copolymers of isobutylene with small amounts of a diolen such as isoprene have created a large demand for suitable plasticizers. Alkyl esters and particularly di-2-ethylhexyl phthalate, di-n-octyl phthalate and tri-2-ethyl-hexyl phosphate have been known to be satisfactory 'plasticizers for the aforementioned high molecular weight materials, but the supply of these plasticizers has been unable to keep pace with the expansion of the plastics industry, largely because of a shortage of alcohols suitable for the manufacture of desired esters.

It is the object of the invention to provide the art with a new source of plasticizers. Another object is the production of plastic compositions having superior physical and chemical properties. Still other objects will appear from. the subsequent description.

It has now been discovered that catalytic cycle gas oil boiling in the range of 545 F. to about 750 F. as well as heavier fractions can be thermally cracked to produce excellent plasticizers. If desired the thermally cracked oil may be concentrated by phenol extraction which may be carried out either batchwise or continuously in a multistage liquid-liquid extraction column. These oils are particularly valuable as partial replacements for the ester type of plasticizer, and are known as thermal tars.

The properties of a plasticizer which are most important are high plasticizing efliciency and low volatility. Usually, when changes are made to improve one of these properties, the other is adversely affected. For example, an increase in alcohol molecular weight in the case of esters such as the phthalates tends to lreduce volatility at the expense of vplasticizing efficiency. However; the mai terials of this invention show the unexpected properties of both low volatility and increased flexibility at low temperatures. The plasticizers of this invention may be used alone in proportions of up to 50 parts by weight per 100 parts of polymer. However, they are more suitably used in conjunction with the usual ester-type plasticizers. In such cases, the plasticizers of the present invention are used in ratios of to l0-parts of the thermal tar to 45 to of the ester type per 100 parts of polymer, .preferably 10 to 20 of the thermal tar to 40 to 30 of the esters. The tar, preferably, has a boiling range between 600 and 780 F. and a'refractive index of about l.56.to 1.65. arrowerf-ractions boiling between 630 and 7 4QfjF. are preferred." Any narrower fractions boiling withinthese limits,-of course, are suitable. If the plastilzizrdpolyvinyl chloride is used in applications involving frequent contact with the skin, it is undersirable to use tar fractions boiling above 740 F. because of possible irritation.

rates Patent For a further understanding of the invention reference may be had to the accompanying drawing in which the single figure is an elevational view generally diagrammatic, showing a flow plan embodying the improvement of the present invention.

Referring specifically to the drawing,v a hydrocarbon petroleum fraction boiling in the gas oil boiling range (380-1000" F.) is introduced into fluidized solids reaction zone 1 by meansof feed line 2. Reactor 1 is filled with a Vfinely divided solid catalyst maintained by conventional means in a pseudo-liquid state by the incoming feed vapors.

The feed is introduced into the catalyst line 3 connecting regenerator 4 Iwith -reactor 1. Temperature and pressure conditions in reactor 1 are adjusted so as to secure the desired conversion of the feed oil.

The temperature can range from 750 to 1050 F. A range of 875 to 950 F. is normally used with 915 F. being typical.

Usuable pressures vary from atmospheric to 200 lbs. Five to 20 lbs. is normal ,with 15 lbs. being a typical exampleall pressures being gauge. A silica-alumina catalyst is used.

Spent catalyst is withdrawn from reactor` 1 by means of line 5y and passed into a iluidized solids regenerator unit 4 wherein temperature and pressure conditions are adjusted to secure the desired .reviviication of the catalyst. Air or oxygen-containing gas is introduced into regenerator 4 by means of lines 6 and 7. Combustion gases areV Withdrawn overhead from regenerato-r 4 by means of line 8. These combustion gases as they flow upwardly in zone 4 contain finely entrained particles of catalyst which particles are removed -by means of cyclone separator uints 9 and 10 disposed in the upper area of zone 4. The iluidized solids cracked products are removed overhead from zone l by means of line 19 and introduced into a distillation zone 20.

Temperature and pressure conditions are adjusted in zone 20 to remove a heavy fraction by means of line 2i1, a heavy gas oil fraction, referred to as heavy catalytic cycle gas oil, -by means of line Z2 and a light gas oil fraction by means of line 23. A fraction boiling in the motor fuel boiling range is removed by means of line 24. Gases are passed upwardly through an absorption section Z5 and .countercurrently contact a downilowing absorption oil which is preferably separated from the light gas oil by means of line 26 and introduced into the top of the absorption section 25. Gas substantially completely free of normally liquid hydrocarbons are removed overhead from zone ZS by means of line 27 and handled as desired. Y j

The heavy fraction is withdrawn through line 2.1 and Vpassed to clarifier 28 where entrained catalyst is settled out and removed through line 29. The clarified oil is Withdrawn through line 30 and introduced into cracking coil 31 housed in furnace 32. Cracked products are withdrawn from furnace 32 through line 33 and introduced into distillation column 34 where temperature and pressure conditions are adjusted to remove a motor fuel fraction as a side stream through line 35 and a heavy tar fraction Vof the desired viscosity by line 36. Light gases are removed overhead through line 37. This heavy tar fraction or cuts thereof Iis the plasticizer of the present invent-ion. If desired the conditions in tower 3'4 may be soV adjusted that the distillation is carried out under vacuum thus increasing the overhead yield and increasing the viscosity of the tar bottoms. Although these bottoms are referred to as tar bottoms, it Iis to be .understood that they are quite fluid. When dark in color they can be converted to light colored materials by distillation. If desired the heavy cycle gas oil from line 2.2 or mixtures i Patented Aug; 9,1960.

of it with the heavy clarified oil from clarifier 28 may be satisfactorily fed to the cracking coil 31.

The conditions obtaining in the thermal cracking zone 31 are conventional and are in the range between 850 F. and l200 `1:". preferably betweenf9'00 F. and 1000ia F. Pressnres may vary from 200 lbs. per square inch to as much as 1'000 lbs. per square inch, preferably between 300 and 800 lbs. per sq. inch.

An alternative to the thermal cracking step is steam cracking, in which case pressures may vary from atmosphen'c to 1000 lbs. and temperature from 1200 to 1600 F.

The effectiveness of the novel materials of this invention as plasticizers is shown in the runs evaluated in Table I wherein a commercial polyvinyl chloride resin known as Geon 101 was chosen as the illustrative material. In preparing the test samples, 100 grams of the resin were dry blended by hand with l gram of lead stearate, 2 grams vanstay, and 25 grams of diisooctyl phthalate as a primary plasticizer. The dry blend was mixed in a beaker with 25 grams of a secondary plasticizer and stirred to give a homogeneous blend whereupon the latter was charged to a 6 x 12 inch laboratory mill heated with steam to about 280 to 320 F. The resin was then fiuxed about two minutes and allowed to mill with a rolling back for ve minutes with occasional cutting.

The sheeted stock was then molded at 280 F. in a standard A.S.T.M. mold (B16-4l) yielding slabs 6 x 6 x 0.075 inch. The molding cycle was 10 minutes at minimum run pressure to allow free ilow of the resin, followed by 10 minutes at 900 lbs./sq. inch. The molded slabs were allowed to stand near 75 F. for at least one day before testing. Several secondary plasticizers were tested in accordance with the above procedure, including the tar of the present invention as Well as tars prepared solely by thermal and catalytic cracking.

The Scott inclined plane tensile tester has been used to measure the stiffness of the compounds at room temperature. Specifically the modulus at 50 and 100% extension is determined -by the application of a load to the specimen by means of a weight which rolls along an inclinable plane. The load is applied at a constant rate regardless of the extensibility of the specimen by tilting the plane at a constant rate. The specimens are die cut from the calendered sheet and are x 0.1 in dimension. These specimens are clamped into the machine, one end being fastened to a fixed member While the other is secured to the rolling weight. The machine has been calibrated to indicate the load for extensions up to 120% and a stress of up to 2250 lb. per square inch. The stress is recorded autographically within these limits and readings are customarily taken at 50% and 100% extensions. An adjustment in the weight of the free rolling member must be made in accordance with the actual gauge of the sheet to permit the direct recording of the stress in curate to .0001" and an average of ve readings is taken before adjustment of the weights is made. By means of this device, measurement ofthe modulus can be made with an accuracy of better than I.0%. The results are summarized 1n Table I.

TABLE I Boiling Refrac- 50% Modulus Material Range, tive in Vinyl l F. Index Heavy Cycle Gas Oil Cut from 580-622 1. 5466 Low Comcatalytic cracking. patibllity.

Do S60-666 1. 5466 Do. D0 695-742 1.5347 D0. Heavy Heating Oil from catalytic 578-652 1. 5372 1915.

cracking. Tar from Thermally Cracking 613-630 1.5694 1735.

above Cycle Gas Oil.

Do 673-684 1. 6002 1465. D0 698-716 1.6097 1415. Tar from Thermal Cracking of 604-740 1.5675 1450.

heavy cycle gas oil from catalytic cracking. Tar (Broad Cut) irom 'lherlnally` 604-740 1.5931 1450.

cracking Mixed Cycle Gas Oll and 1Cllaritled Oil from catalytic crackg. Do EEO-734 1.5892 1520. Tar from Thermal Cracking cf 680-740 1. 5574 1726.

Virgin Naphtha.

a Recipe: Vinyl resin 100, Vanstay 2, Lead stearate 1, Dllsoocyl phthalate (DIOP) 25, Secondary plasticizer 25.

From the above data it is evident that thermal cracking of a catalytic cycle stock or clarified oils give oils of good plasticizing efficiency. Thermal tar from cracking of virgin naphtha is not as eective as the tar from catalytic stocks as is evident from the higher modulus. The better plasticizers give the lower moduli figures, Le., they render the polymer more exible which is very desirable in the case of polyvinyl chloride. The thermal tar from catalytic stocks contains more complex ring structures and less alkyl side chains as evidenced by the diierence in refractive index.

Similar results are obtained when employing a stock which has been prepared by the thermal cracking of an oil obtained by catalytic cracking and then concentrated by solvent extraction ywith phenol, liquid SO2 or methanol or other suitable solvent. Table II gives results obtained with a cycle oil from catalytic cracking which was subjected to subsequent thermal cracking and then phenol extracted at a 3/1 solvent/ oil ratio and 15% water in phenol as the solvent to give a 54.7% yield of extract which had a refractive index of 1.6330. This material was tested as obtained and also in l0 fractions.

lbs/sq. in. The thickness is measured with a gauge ac- The results are shown in Table II.

TABLE lll The effect of boiling range on plasticizer efficiency of thermal tar in vinyl compounds a Cuts obtained by iractionating in a 15 plate Oldershaw column at a reflux ratio 013 to 1. b Recipe: Vinyl resin 100, Vanstay 2, Lead stearate 1, diisooctyl phthalate 25, Oil 25.

The above data show that the extract is an eicient plasticizer `for vinyl resins.

However, considerable improvement in efficiency can be obtained by discarding both the lighter ends and the parts of a wax-free, asphaltenefree heavy tar; said heavy tar being prepared by providing a hydrocarbon petroleum fraction with a boiling range of about 380 to 1000 F.; cracking said hydrocarbon petroleum fraction in the heavier ends. A good eiciency is obtained at about 600 5 presence of a nely divided silica-alumina catalyst at a to 780 F. boiling range and a refractive index of about temperature between about 750 and 1050 F.; distilling 1.60 to 1.65. The optimum fraction has a boiling range lsaid cracked petroleum fraction to produce a heavy, gasof about 630 to 740 F. Any fraction within this range oil fraction boiling in the range of about 545 to 750 F.; is suitable. 1f the plasticized polyvinyl chloride is used subjecting said heavy, gas-oil fraction to thermal cracking in applications involving frequent contact with the skin, Aat a temperature between 850 and 1200 F.; and disfractions boiling above about 740 F. are undesirable. tlling said cracked gas-oil fraction to produce said heavy They may cause irritation of the skin upon sufficiently tar with a boiling range between about 600 and 780 F. long contact. and a refractive index between about 1.56 and 1.65.

Even better results can be obtained by blending the 3. A composition of matter with increased exibility highest and lowest cuts. Table III gives results obtained comprising 100 parts of polyvinyl chloride, 10 to 45 parts with a cycle oil from catalytic cracking which was then of an alkyl ester selected from the group consisting of thermally cracked, phenol extracted and fractionated and di-2-ethylheXyl phthalate, di-Ilootyl phthalate, tli-Zetllyl the lowest and highest cuts reblended. hexyl phosphate, and mixtures thereof, and 5 to 40 pants TABLE Percent 50% Inclined Plane Torsional Modulus X 10-3 Boiling Plast. Modulus Material Range, Loss on F. Milling 1 Day 7 Days 4Weeks +25 +15 0 -15 25 O.

Therme! Tar Extract:

1. Wide out 44a-825 13.5 1400 1710 5.0 27.4 132.5 285 347 2. Lowest ontw-. 5224140 22.2 1385 1555 1560 5.6 22.5 117.4 225.0 300.0 3. Highest Cut 785-820 5.0 1535 1570 1780 5.4 29.4 139.5 270.0 349.0 4. Blend of equal parts of 2 and 3 6.8 1330 1530 3.7 16.0 104 237 300 The terms thermal cracking and thermally crackof a wax-free, lasphaltene-free heavy tar; said heavy tar ing if employed in the claims are defined to include conbeing prepared by providing a hydrocarbon petroleum ventional thermal cracking and also thermal cracking in fraction with a boiling range of about 380 to 1000 F.; ythe presence of steam which is often referred to as steam efaekillg Said hyfifoeafbotl Petfolellll"i ffaetion in the cracking. presence of a nely divided silica-alumina catalyst at a Obviously resort may be had to various modifications temperature between 'about 750 and 1050 F4 distillillg and variations without departing from the spirit of the Said cracked petroleum fraction t0 produce a heavy, gasinvention or the Scope of the appended claims, 40 oil fraction boiling in the range of about 545 to 750 iF.; The nature of the present invention having been thus Sllhieetiflg Said heal/'Yi gas-oil fraction "t0 thermal eraekgenerally set yforth and specific examples of the same ing at 'a temPeIatUIe between about 850 and 1200 F- given, what is claimed as new and useful and desired to diStilliIlg `Said Cracked gas-oil fraction t0 Produce Said be secured by Letters Patent is; heavy tar with a boiling range lbetween -about 600 and l. A composition of matter with increased flexibility 780 F. and a refractive index between about 1,56 and comprising polyvinyl chloride and a Wax-free, asphaltene- L65- free heavy tar; said heavy tar being prepared by pro 4- A Composition of matter aoeol'dillg to Claim 3 in viding -a hydrocarbon petroleum fraction with a boiling Which the alkyl ester is di-n-octyl phthalaterange of about 380 yto 1000 F.; cracking said hydro- 5- A Composition 0f matter according to Claim 3 in carbon petroleum fraction at a temperature between 750 50 Which the alkyl eSteI' iS iii-Z-etllylheXYl phthalate. Iand l050 F. in the presence of -a nely divided silic-a- 6- A Composition of matter 'according to olaiml 3 ill alumina catalyst; distilling said cracked petroleum frac- Which the alkyl ester iS tli-Z-ethylhexyl Phosphatetion to produce a heavy, gas-oil fraction boiling in the v range of about 545 to 750 F.; subjecting said heavy, References Cited i-o the ille of this Patent gas-011 fraction to thermal cracking at a temperature be- UNITED STATES PATENTS tween labout 850 and 1200 F.; and distilling said cracked, gas-oil fraction to produce said heavy tar with a boiling range between about 600 and 780 F. and a refractive index between about 1.56 and 1.65.

2. A composition of matter with increased exibility 2,464,219 Doyle et al. Mar. 15, 1949 2,698,280 Hersberger et al. Dec. 28, 1954 FOREIGN PATENTS 562,956 Great Britain .Tilly 24, 1944 

3. A COMPOSITION OF MATTER WITH INCREASED FLEXIBILITY COMPRISING 100 PARTS OF POLYVINYL CHLORIDE, 10 TO 45 PARTS OF AN ALKYL ESTER SELECTED FROM THE GROUP CONSISTING OF DI-2-ETHYLHEXYL PHTHALATE, DI-N-OCTYL PHTHALATE, TRI-2-ETHYLHEXYL PHOSPHATE, AND MIXTURES THEREOF, AND 5 TO 40 PARTS OF A WAX-FREE, ASPHALTENE-FREE HEAVY TAR, SAID HEAVY TAR BEILNG PREPARED BY PROVIDING A HYDROCARBON PETROLEUM FRACTION WITH A BOILING RANGE OF ABOUT 380* TO 1000* F., CRACKING SAID HYDROCARBON PETROLEUM FRACTION IN THE PRESENCE OF A FINELY DIVIDED SILICA-ALUMINA CATALYST AT A TEMPERATURE BETWEEN ABOUT 750* AND 1050* F., DISTILLING SAID CRACKED PETROLEUM FRACTION TO PRODUCE A HEAVY, GASOIL FRACTION BOILING IN THE RANGE OF ABOUT 545* TO 750* F., SUBJECTING SAID HEAVY, GAS-OIL FRACTION TO THERMAL CRACKING AT A TEMPERATURE BETWEEN ABOUT 850* AND 1200* F., DISTILLING SAID CRACKED GAS-OIL FRACTION TO PRODUCE SAID HEAVY TAR WITH A BOILING RANGE BETWEEN ABOUT 600* AND 780* F. AND A REFRACTIVE INDEX BETWEEN ABOUT 1.56 AND 1.65. 